Catalyst exhibiting hydrogen spillover effect

ABSTRACT

The catalyst exhibiting hydrogen spillover effect relates to the composition of a catalyst exhibiting hydrogen spillover effect and to a process for preparing the catalyst. The catalyst has a reduced transition base metal of Group VIB or Group VIIIB, such as cobalt, nickel, molybdenum or tungsten, supported on a high porous carrier, such as saponite, the base metal being ion-exchanged with at least one precious metal of Group VIIIB. The process includes the steps of loading the base metal onto the support, reducing the base metal, preferably with H 2  at 600° C., and thereafter ion-exchanging the precious metal with the base metal. Preferred examples of the catalyst include a saponite support loaded with about 10-20 wt % cobalt and about 0.1-1 wt % precious metal. The catalyst is optimized for reactions that occur in commercial processes at about 360-400° C., such as in hydrocracking.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to catalysts used for hydrocracking, hydrodesulfurization, hydrodenitrogenation, transalkylation, disproportionation, hydrogenation, and alkylation, and particularly to a catalyst exhibiting hydrogen spillover effect to enhance catalytic efficiency.

2. Description of the Related Art

Many organic reactions require the addition of hydrogen, particularly in petroleum refining. Hydrocracking, for example, is a process that is used to produce gasoline, diesel fuel, and jet fuel from aromatic feedstocks. The process requires the addition of hydrogen at high pressure to add hydrogen to aromatic centers, and an acid-catalyzed cracking of paraffinic side chains on the aromatic molecules. In addition, nitrogen and sulfur must be removed from the feedstock to avoid acid-base reactions with the acid catalyst used to crack the paraffinic side chains. This is typically accomplished by hydrodenitrogenation (adding hydrogen to the feedstock before introduction to the cracking reactor) to form ammonia) and hydrodesulfurization (adding hydrogen to the feedstock before introduction to the cracking reactor to form hydrogen sulfide).

Nevertheless, molecular hydrogen is not very reactive. In order to speed the reaction, hydrocracking reactors use a catalyst to break the molecular hydrogen down to atomic hydrogen. The catalyst used to activate the hydrogen is generally a metal, which may be a noble or precious metal, or may be molybdenum, tungsten, nickel, iron, or the like. The catalyst for a hydrocracking reactor is typically an acidic zeolyte bed loaded with the metal catalyst.

However, the conventional hydrocracking reactor bed separates the site of activated hydrogen from the acidic cracking sites. It has been noted that some specially constructed beds exhibit an effect known as hydrogen spillover, in which the activated atomic hydrogen spills over into the pores of the support bed. It is thought that this speeds the process of reduction of the aromatic hydrocarbon centers, as well as saturating olefinic side chains. Some catalysts have also been developed to utilize this effect to selectively promote desired reactions, and in the development of hydrogen fuel cells.

Several of the present inventors described a catalyst exhibiting hydrogen spillover effect in an article published in Applied Catalysis A. General, Vol. 277, Issues 1-2, pp. 63-72 in March 2002, which is hereby incorporated by reference. The catalyst described therein generally comprised a smectite clay having rhodium impregnated over the clay by incipient wetness method, which was then ion-exchanged with cobalt nitrate to produce a clay catalyst having 20 wt % CoO and 1 wt % rhodium. The catalyst was compared to a similar catalyst without the noble metal and to a commercial hydrocracking catalyst by a procedure known as Temperature-Programmed Reduction (TPR), which measures the total amount of hydrogen consumed as a function of temperature, and which allows calculation of the degree of reduction and the temperature at which different species are reduced. TPR is a technique sometimes used to measure hydrogenation and hydrogen spillover effects. See “Selective Hydrogenation of Cinnamaldehyde With Pt and Pt—Fe Catalysts: Effects of the Support,” A. B. daSilva et al., Braz. J. Chem. Eng., Vol. 15, No. 2 (1998), pp. 140-144.

Nevertheless, due to the expense of precious or noble metals and the need to moderate temperatures in various organic reactions, such as those taking place during hydrocracking, there is a need to obtain greater efficiency in catalysts exhibiting hydrogen spillover effect.

None of the above publications, taken either singly or in combination, is seen to describe the instant invention as claimed. Thus, a catalyst exhibiting hydrogen spillover effect solving the aforementioned problems is desired.

SUMMARY OF THE INVENTION

The catalyst exhibiting hydrogen spillover effect relates to the composition of a catalyst exhibiting hydrogen spillover effect and to a process for preparing the catalyst. The catalyst has a reduced transition base metal of Group VIB or Group VIIIB, such as cobalt, nickel, molybdenum or tungsten, or an oxide or sulfide thereof, supported on a high porous carrier, such as saponite, the base metal being ion-exchanged with at least one precious metal of Group VIIIB. The process includes the steps of loading the base metal on the support, reducing the base metal, preferably with H₂ at 600° C., and thereafter ion-exchanging the precious metal with the base metal. Preferred examples of the catalyst include a saponite support loaded with about 10-20 wt % cobalt and about 0.1-1 wt % precious metal. The catalyst is optimized for reactions that occur in commercial processes at about 360-400° C., such as in hydrocracking.

These and other features of the present invention will become readily apparent upon further review of the following specification and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart diagrammatically illustrating preparation of test catalysts for a catalyst exhibiting hydrogen spillover effect according to the present invention.

FIG. 2 is a graph showing temperature programmed reduction results for the test catalysts of FIG. 1.

Similar reference characters denote corresponding features consistently throughout the attached drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to a catalyst exhibiting hydrogen spillover effect and to a process for preparing the catalyst. The catalyst accelerates reactions requiring the addition of hydrogen, including hydrocracking, hydrodesulfurization, hydrodenitrogenation, transalkylation, disproportionation, hydrogenation, and alkylation. Examples are provided that particularly accelerate reactions that are involved in processes occurring between about 360° C. and 400° C.

The catalyst has a reduced transition base metal of Group VIB or Group VIIIB, such as cobalt, nickel, molybdenum or tungsten, or an oxide or sulfide thereof, supported on a high porous carrier, such as magnesium silicate-based clay, preferably saponite, the base metal being ion-exchanged with at least one precious metal of Group VIIIB, preferably rhodium, palladium, and/or platinum. The process includes the steps of loading the base metal on the support, reducing the base metal, preferably with H₂ at 600° C., and thereafter ion-exchanging the precious metal with the base metal. Preferred examples of the catalyst include a saponite support loaded with about 10-20 wt % cobalt and about 0.1-1 wt % precious metal. The catalyst is optimized for reactions that occur in commercial processes at about 360-400° C., such as in hydrocracking.

As used herein, the term “reduced” means that at least a portion of the metal ions, metallic salts, or the metal ions deposited on the porous support have been reduced to the metallic state.

More particularly, there is selected a clay support, preferably saponite, and, more preferably, high pore saponite, which has a surface area between 130 and 650 m²/g, preferably between 400 and 600 m²/g, and which has a total pore volume between 0.4 and 0.8 ml/g, preferably between 0.45 and 0.75 ml/g. Preparation of test catalysts exhibiting hydrogen spillover effect was carried out using the saponite clay support loaded with active metals of Group VIII preferably cobalt, rhodium and palladium. These metals are loaded on the support with the specified configuration to achieve the desired hydrogen spillover effects. That is to say, rhodium is selectively loaded by the ion-exchange method onto the main catalyst component cobalt particles and palladium particles, which are located independently from cobalt particles.

The following examples describe preparation of the various test catalysts.

EXAMPLE 1 Type A

The high pore saponite (HPS) described above was placed in contact with an aqueous solution containing a soluble salt corresponding to the base metal of Group VIII of the Periodic Table, more particularly, cobalt, for a period of between 1 and 5 hours, between 3 and 5 hours being preferable, during which it is desired to deposit cobalt onto the support with the object of obtaining a composition including between 10 and 20% by weight of the base metal of Group VIII on the clay support, based on the dry weight of the final catalyst.

At the end of the specified impregnation time, the clay support, now impregnated with the active metal, that is to say, with the base metal of Group VIII, was filtered, dried in the air circulation oven for a period between and 30 hours, between 8 and 24 hours being preferable, at a temperature between 25° C. and 180° C., between 60° C. and 150° C. being preferable, and finally calcined at a temperature between 400° C. and 700° C., between 450° C. and 650° C. being preferable, for a period between 0.5 and 24 hours, between and 12 hours being preferable, using dry air. H₂ treatment at 600° C. was made thereafter, as shown diagrammatically in FIG. 1, but only 10% of the CoO was reduced, as estimated from the TPR tracing 10 of the Type A catalyst shown in FIG. 2. The TPR tracing 10 corresponds to about 18 wt % cobalt oxide deposited on the high porous support (HPS).

EXAMPLE 2 Type B

The high pore saponite described above was placed in contact with an aqueous solution containing a soluble salt corresponding to the precious metal of Group VIII of the Periodic Table, more particularly, palladium, for a period of between 1 and 5 hours, between 3 and 5 hours being preferable, during which it is desired to deposit palladium onto the support with the object of obtaining a composition including between 1 and 2% by weight of the precious metal Group of Group VIII on the clay support, based on the dry weight of the final catalyst.

At the end of specified impregnation time, the clay support, impregnated with the precious metal of Group VIII, was filtered, dried in the air circulation oven for a period between 5 and 30 hours, between 8 and 24 hours being preferable, at a temperature between 25° C. and 180° C., between 60° C. and 150° C. being preferable, and finally calcined a temperature between 400° C. and 700° C., between 450° C. and 650° C. being preferable, for a period between 0.5 and 24 hours, between 1 and 12 hours being preferable, using dry air. Palladium oxide on the support was reduced to the metallic state.

The saponite based catalyst loaded with palladium was then impregnated with a base metal belonging to Group VIII, more particularly, with cobalt as a soluble salt, to obtain a preferred composition including between 1 and 20% cobalt by weight as the oxide, based on the dry weight of the final catalyst. H₂ treatment at 600° C. was made thereafter, the preparation being diagrammatically shown as Type B in FIG. 1. About 40% of the CoO could be reduced by this treatment, as estimated from the TPR tracing 20 of the Type B catalyst shown in FIG. 2. The TPR tracing 20 corresponds to about 18 wt % loaded onto about 1.0 wt % palladium ion-deposited on the high porous support (HPS).

EXAMPLE 3 Type C

The clay support of high pore saponite described above was placed in contact with an aqueous solution containing a soluble salt corresponding to the base metal of Group VIII of the Periodic Table, namely, with cobalt, for a period of between 1 and 5 hours, between 3 and 5 hours being preferable, during which it is desired to deposit cobalt onto the support with the object of obtaining a composition including between 10 and 20% by weight of the base metal Group of Group VIII on the clay support, based on the dry weight of the final catalyst.

At the end of specified impregnation time, the clay support impregnated with the cobalt was filtered, dried in the air circulation oven for a period between 5 and 30 hours, between 8 and 24 hours being preferable, at a temperature between 25° C. and 180° C., between 60° C. and 150° C. being preferable, and finally calcined a temperature between 400° C. and 700° C., between 450° C. and 650° C. being preferable, for a period of between 0.5 and 24 hours, between 1 and 12 hours being preferable, using dry air. The cobalt-loaded support was treated by H₂ at 600° C., but only 10 wt % of CoO was reduced, similar to the result obtained in Type A of Example 1.

The saponite-based catalyst loaded with cobalt oxide was impregnated with a precious metal belonging to Group VIII, namely, with rhodium as a soluble salt, to achieve obtaining a preferred composition including between 0.1 and 1.0% by weight as oxide, based on the dry weight of the final catalyst. H₂ treatment at 600° C. was made thereafter, as indicated diagrammatically for the Type C catalyst in FIG. 1. Almost total reduction of CoO occurred, as estimated from the TPR tracing 30 of Type C in FIG. 2, due to the hydrogen spillover effect of rhodium. The TPR tracing 30 corresponds to about 1.0 wt % rhodium ion-exchanged with about 18 wt % cobalt oxide loaded onto the high porous support (HPS).

EXAMPLE 4 Type D

The clay support of high pore saponite described above was placed in contact with an aqueous solution containing a soluble salt corresponding to the precious metal of Group VIII of the Periodic Table, namely, with palladium, for a period of between 1 and 5 hours, between 3 and 5 hours being preferable, during which it is desired to deposit palladium onto the support with the object of obtaining a composition including between 1 and 2% by weight of the precious metal Group of Group VIII on the clay support, based on the dry weight of the final catalyst.

At the end of the specified impregnation time, the clay support impregnated with the precious metal of Group VIII was filtered, dried in the air circulation oven for a period between 5 and 30 hours, between 8 and 24 hours being preferable, at a temperature between 25° C. and 180° C., between 60° C. and 150° C. being preferable, and finally calcined a temperature between 400° C. and 700° C., between 450° C. and 650° C. being preferable, for a period of between 0.5 and 24 hours, between 1 and 12 hours being preferable, using dry air. The palladium-loaded saponite was reduced by H₂ at 600° C. to convert the palladium into the metallic state.

The saponite-based catalyst loaded with palladium was then impregnated with a base metal belonging to Group VIII, namely, cobalt as a soluble salt, to obtain a preferred composition including between 1 and 20% cobalt by weight as the oxide, based on the dry weight of the final catalyst. The palladium and CoO loaded saponite was treated with H₂ at 600° C., and about 40% of the CoO was reduced by this treatment.

This was ion-exchanged with a precious metal belonging to Group VIII, namely, with rhodium as a soluble salt at about 0.1 wt %, a composition including between 0.1 and 1.0% by weight as the oxide being preferred, based on the dry weight of the final catalyst. Rhodium was selectively loaded onto the reduced cobalt part, as shown diagrammatically in FIG. 1, and exhibits prominent hydrogen spillover effect. As the result, major parts of the catalyst components could be reduced at just the same temperature range that is preferred in catalytic hydrocracking reactions, as shown by the TPR trace 40 of the Type D catalyst in FIG. 2. The TPR trace 40 corresponds to about 0.1 wt % rhodium ion-exchanged with cobalt and palladium formed by reduction of about 18 wt % cobalt oxide loaded onto about 1.0 wt % palladium loaded onto the high porous support (HPS).

The catalysts prepared in the above-mentioned Examples 1 to 4 were evaluated under the Temperature Programmed Reduction (TPR) technique to determine the temperature at which these catalysts can be reduced to the metallic state under the conditions of the experiments. The procedures for pretreatment and subsequent TPR experiments were as follows. The catalyst sample was pretreated in a quartz tube reactor at about 400° C. maintained for 2 to 4 hours in flowing dry air having 30 to 50 cm³/min rates. The gas mixture used for reduction was 5% H₂ in argon. The temperature of the reactor was then increased linearly from room temperature to about 1,100° C. at a heating rate of 10° C./min and then maintained isothermally for 15 minutes. The hydrogen gas consumed with increasing temperature was determined using a thermal conductivity detector.

A catalyst expected to exhibit the hydrogen spillover effect can be shown by the decrease in the temperature programmed reduction temperature of the catalysts. This phenomenon is shown in FIG. 2, and the reduction temperature data is given in Table I, below. The data shows a marked decrease in the reduction temperature of the high pore saponite (HPS)-based catalysts having precious metal due to the hydrogen spillover effect.

TABLE I Comparison of peak temperatures on TPR profiles Temp. Peak Decrease in range of temp. of peak temp. main TPR main from Catalyst profile profile reference Type Catalyst features (° C.) (° C.) (° C.) A 18 wt % CoO/HPS 550~850 726 — B 1.0 wt % Pd + 18 wt % 380~800 633  93 (Co + CoO)/HPS C 18 wt % CoO/HPS 380~600 447 279 and then 1.0 wt % Rh loaded D (1.0 wt % Pd; after 320~460 373 353 H₂ reduction, 18 wt % CoO/HPS); after H₂ treatment at 600° C., 0.1 wt % Rh was loaded selectively on the reduced CoO parts (may be Co) by ion exchange

In Table I, the initiation temperature and the termination temperature are decided by extrapolation of the profiles of the main ascending and descending curves, respectively.

In the presence of 1.0 wt % Pd on 18 wt % CoO/HPS, the reduction temperature decreased from 726° C. to 633° C. compared by peak temperature of TPR profiles. When 1.0 wt % Rh was loaded on 18 wt % CoO/HPS, the reduction temperature was further decreased to 477° C. This effect of temperature reduction was furthermore exhibited by the loading of only 0.1 wt % Rh onto the 1.0 wt % Pd and 18 wt % (Co+CoO)/HPS catalyst. In this case, reduction temperature was reduced to 373° C., which just coincides with the reaction temperature range desired for hydrocracking reactions.

The TPR traces 30 and 40 show higher, narrower peaks as compared with the TPR traces 10 and 20 of FIG. 2, and as compared to the TPR traces of FIG. 1 at page 67 of the publication Applied Catalysis A. General, Vol. 277 (2002), cited above, indicating that the Type C and Type D catalysts produce significantly more efficient hydrogen reduction. In addition, the Type D catalyst produced peak reduction squarely within a preferred temperature range for operating a hydrocracking reactor to catalyze reactions occurring therein.

The process for preparing a catalyst exhibiting hydrogen spillover effect may be said to include the steps of: (a) loading a water soluble salt of a base metal onto a porous support, preferably sufficient to obtain between about 10 wt % to 20 wt % by dry weight of the catalyst; (b) reducing the base metal, preferably with H₂ at about 600° C.; and (c) ion-exchanging the base metal with at least one precious metal, preferably to between about 0.1 wt % to 1 wt % by dry weight of the catalyst.

The method may further comprise the steps of loading a first precious metal onto the porous support, preferably to about 1 wt % of the first precious metal in the total dry weight of the catalyst, and reducing the first precious metal, preferably by H₂ at about 600° C., prior to step (a), step (c) then comprising ion-exchanging the base metal with a second precious metal to obtain about 0.1% of the second precious metal in the total dry weight of the catalyst. In the foregoing method, the base metal is preferably molybdenum, tungsten, nickel or cobalt, more preferably cobalt, and the precious metal is preferably palladium, rhodium, and/or platinum. The present invention also extends to a catalyst produced by the foregoing process.

It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims. 

1. A catalyst exhibiting hydrogen spillover effect, comprising: a porous support; a reduced base metal selected from the group of transition metals of Group VIB and Group VIIIB loaded on the porous support; and at least two precious metals of Group VIIIB ion-exchanged with the reduced base metal.
 2. The catalyst according to claim 1, wherein said porous support comprises saponite clay.
 3. The catalyst according to claim 1, wherein said porous support has a surface area between 130 and 650 m²/g and a total pore volume between 0.4 and 0.8 ml/g.
 4. The catalyst according to claim 1, wherein said porous support has a surface area between 400 and 600 m²/g and a total pore volume between 0.45 and 0.75 ml/g.
 5. The catalyst according to claim 1, wherein said reduced base metal is a base metal selected from the group consisting of molybdenum, tungsten, cobalt and nickel.
 6. The catalyst according to claim 1, wherein said reduced base metal comprises cobalt.
 7. The catalyst according to claim 1, wherein said reduced base metal comprises between about 10 wt % and about 20 wt % of the catalyst by dry weight as the reduced metal and oxides and salts thereof.
 8. The catalyst according to claim 1, wherein said at least two precious metals are selected from the group consisting of palladium, rhodium, and platinum and water soluble salts and oxides thereof. 9-10. (canceled)
 11. The catalyst according to claim 1, wherein said at least two precious metals comprise: reduced palladium, said reduced base metal being loaded thereon; and rhodium and water soluble salts and oxides thereof ion-exchanged with said reduced base metal and the reduced palladium.
 12. The catalyst according to claim 1, wherein said at least two precious metals comprise between about 0.1 wt % and 2 wt % of the catalyst by dry weight.
 13. (canceled)
 14. The catalyst according to claim 1, wherein said reduced base metal comprises between about 10 wt % and 20 wt % cobalt by dry weight of the catalyst and said at least two precious metals comprise: about 1 wt % reduced palladium, said reduced base metal being loaded thereon; and about 0.1 wt % rhodium and water soluble salts and oxides thereof by dry weight of the catalyst ion-exchanged with the reduced palladium and said reduced base metal.
 15. The catalyst according to claim 1, wherein said reduced base metal comprises between about 10 wt % and about 20 wt % of the catalyst by dry weight, and said at least two precious metals comprise between about 0.1 wt % and 1 wt % by dry weight of the catalyst. 16-20. (canceled)
 21. A catalyst exhibiting hydrogen spillover effect, comprising: a porous support; a water soluble salt of cobalt loaded on the porous support, the water soluble salt of cobalt being reduced; palladium loaded on the porous support, the palladium being reduced by H₂ at about 600° C. prior to loading on the porous support, the reduced palladium forming between about 1 wt % and 2 wt % by dry weight of the catalyst; and rhodium or water soluble salts or oxides thereof ion-exchanged with the reduced cobalt salt and the reduced palladium and forming about 0.1% by dry weight of the catalyst.
 22. A catalyst exhibiting hydrogen spillover effect, comprising: a porous support; a water soluble salt of a base metal loaded on the porous support, the water soluble salt of the base metal being reduced; a first precious metal loaded on the porous support, the first precious metal being reduced by H₂ at about 600° C. prior to loading on the porous support, the reduced first precious metal forming between about 1 wt % and 2 wt % by dry weight of the catalyst; and a second precious metal or water soluble salts or oxides thereof ion-exchanged with the reduced base metal and the reduced first precious metal and forming about 0.1% by dry weight of the catalyst. 23-31. (canceled) 